JP3259465B2 - Ring-opening (co) polymer cyclized hydrogenated product, production method thereof, and use thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to transparency, low birefringence,
The present invention relates to a thermoplastic phenyl-norbornene-based ring-opening (co) polymer cyclized hydrogenated product excellent in light resistance, low dielectric constant, low dielectric loss, chemical resistance, and the like, a method for producing the same, and its use.

[0002]

2. Description of the Related Art Ring opening (co) of phenyl-norbornenes
Cyclized products having excellent heat resistance obtained by treating a polymer with a Lewis acid or Bronsted acid are known (JP-A-50-154399). However, little was known about the optical and electrical properties of this resin.

[0003] On the other hand, if the cyclization ratio is too high, the mechanical strength is reduced, and it has been very difficult to use as a molding material. On the other hand, if the cyclization ratio is too low, a large number of double bonds derived from the monomer remain in the cyclized product main chain, so that there is a problem that the oxidization deterioration resistance and the light deterioration resistance are poor.

When a general resin has an unsaturated bond in a main chain structure and is liable to be deteriorated by air oxidation or the like,
It is known that the hydrogenation treatment saturates unsaturated bonds in the main chain structure to make it less likely to deteriorate (for example, Japanese Patent Publication No. 2-9619). However, as for the ring-opened (co) polymer cyclized product of phenyl-norbornenes, no hydrogenated product was known, and it was not known what kind of optical or electrical properties the hydrogenated product had. .

[0005]

The present inventors have made intensive efforts to develop a novel resin having low birefringence, and as a result, have obtained a cyclized product of a ring-opened (co) polymer of phenyl-norbornenes. The novel phenyl-norbornene ring-opening (co) polymer cyclized hydrogenated product obtained by hydrogenation is hardly oxidized in air and has excellent optical and electrical properties such as low birefringence. We have found and completed the present invention.

[0006]

Thus, according to the present invention, a phenyl-norbornene ring-opening (co) polymer is cyclized to the extent that 10% or more of the main-chain double bond remains, A ring-opened (co) polymer cyclized hydrogenated hydrogenated ring-opening (co) polymer of phenyl-norbornene and a hydrogen-opened (co) polymer of phenyl-norbornene so that the residual ratio of the bond is 5% or less. A method for producing the cyclized hydrogenated product of the ring-opened (co) polymer, in which the cyclized product is hydrogenated so that the residual ratio of the double bond in the main chain of the polymer is 5% or less after cyclization in the remaining range, and Uses of the ring-opened (co) polymer cyclized hydrogenated product are provided.

(Phenyl-norbornenes) The phenyl-norbornenes which are monomers used in the present invention are at least one kind of a norbornene derivative containing a phenyl group or a substituted phenyl group at the 2- and / or 3-position. A compound of the general formula 1

Embedded image (Wherein, R ^{1 to} R ^{9 each} represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a halogen group, an alkoxy group, a polar group such as a cyano group, or a C ^{1 to} C ⁹ substituted with these polar groups. 4 represents a hydrocarbon group). Specifically, for example,
2-phenyl-5-norbornene, 2- (2'-methylphenyl) -5-norbornene, 2-phenyl-3-methyl-5-norbornene, 2-phenyl-2-methyl-
5-norbornene, 2- (4'-chlorophenyl) -5
-Norbornene, 2- (2'-carbethoxyphenyl) -5-norbornene, 2-phenyl-2-cyano-
5-norbornene and the like.

(Comonomer) As long as the object of the present invention is not impaired, those which can be subjected to metathesis polymerization, such as norbornenes and cycloalkenes, other than those represented by the general formula 1, may be used as the comonomer. Specifically, 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene,
5-butyl norbornene, 5-ethyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-methoxycarbonyl 2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2
-Norbornene, 5-hexyl-2-norbornene,
5-octyl-2-norbornene, 5-octadecyl-
Norbornene such as 2-norbornene, its alkyl,
Alkylidene, alkenyl, their halogen, hydroxyl group, ester group, alkoxy group, cyano group, amide group,
1,4: 5, a polar group substituent such as an imide group or a silyl group;
8-Dimethano-1,4,4a, 5,6,7,8,8a-
Octahydronaphthalene, 6-methyl-1,4: 5,8
-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethyl-1,4: 5,8-
Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4: 5,8
-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-methyl-6-methoxycarbonyl-1,4: 5,8-dimetano-1,4,4a,
5,6,7,8,8a-octahydronaphthalene, 6-
Cyano-1,4: 5,8-dimetano-1,4,4a,
Monomers, such as 5,6,7,8,8a-octahydronaphthalene, to which norbornene is added one or more cyclopentadiene, and derivatives and substituents similar to the above; dicyclopentadiene, 2,3-dihydrodiene Norbornene derivatives such as dicyclopentadiene derivatives such as cyclopentadiene; cyclobutene, cyclopentene, cyclooctene, 1,5-cyclooctadiene, 1,5,9-
Cycloalkenes such as cyclodecatriene; and the like.

(Polymerization) Polymerization of the monomer composition may be a ring-opening polymerization method using a known metathesis polymerization catalyst, and is not particularly limited. For example, the method described in JP-A-50-154399 and JP-A-60-26024 may be used.

(Ring-opened (co) polymer) In the ring-opened (co) polymer used in the present invention, a compound represented by the general formula 2

Embedded image (Wherein, R ^{1 to} R ^{9 each} represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a halogen group, an alkoxy group, a polar group such as a cyano group, or a C ^{1 to} C ⁹ substituted with these polar groups. Of the phenyl-norbornenes represented by the formula (4), wherein the norbornene ring of the phenyl-norbornenes is opened in an amount of 10 to 100 mol%, preferably 2 to 100 mol%, of all the repeating structural units.
5 to 100 mol%, more preferably 40 to 100 mol%
It is. When the number of repeating structural units in which the phenyl-norbornenes are opened is too small, the improvement in heat resistance due to cyclization is small. In the case where a plurality of types of phenyl-norbornenes are used or in the case where other metathesis-polymerizable comonomers are used, the reactivity of the monomers is different. A difference may occur in the ratio of the monomer in the monomer composition used for the polymerization reaction. In such a case, the above structure is obtained by changing the ratio of the monomers in the monomer composition.

(Cyclization reaction) In the present invention, cyclization means that a repeating structural unit represented by the general formula (2) is

Embedded image (Wherein, R ^{1 to} R ^{9 each} represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a halogen group, an alkoxy group, a polar group such as a cyano group, or a C ^{1 to} C ⁹ substituted with these polar groups. 4 represents a hydrocarbon group).

The method for cyclizing the ring-opened (co) polymer used in the present invention is not particularly limited, and is disclosed in JP-A-50-154399.
A known method using an acidic compound described in Japanese Patent Application Laid-Open Publication No. H10-209, 1988 may be used.
The acidic compound is a Lewis acid or a Bronsted acid, specifically, AlCl ₃ , AlBr ₃ , BF ₃ , B
F ₃ OEt ₂ , BBr ₃ , BBr ₃ OEt ₂ , TiCl ₂ , T
iBr ₄ , TiI ₄ , FeCl ₃ , FeCl ₂ , SnC
l ₂ , SnCl ₄ , WCl ₆ , MoCl ₅ , SbCl ₅ , T
Periodic Tables such as eCl ₂ Metal halide compounds from Groups IIIA to VIII; Hydrogen acids such as HCl, HF, HBr; H ₂ SO ₄ , H ₃ BO ₃ , HClO ₄ , CH ₃ COO
H, H ₃ PO ₄ , P ₂ O ₅ , oxo acids such as p-toluenesulfonic acid, and high-molecular compounds such as ion-exchange resins having anions constituting them; CH ₂ ClCOOH, C
Halogenated acetic acids such as HCl ₂ COOH and CCl ₃ COOH; Heteropoly acids such as phosphomolybdic acid and phosphotungstic acid; SiO ₂ , Al ₂ O ₃ , SiO ₂ —Al ₂ O ₃ , Mg
_{O-SiO 2, B 2 O} 3 -Al 2 O 3, WO3-Al 2 O 3,
_{Zr 2 O 3 -SiO 2, H} + or zeolites exchanged with rare earth, activated clay, acid _{clay, γ-Al 2 O 3,} P 2 O 5
And a solid acid such as solid phosphoric acid in which diatomaceous earth is supported. These may be used in combination, and when the activity of the acidic compound can be improved by adding another compound or the like, such a compound may be added. For example, compounds that improve the activity of metal halide compounds as acidic compounds include Me
Metal alkyl compounds such as Li, EtLi, BuLi, and Me ₄ Sn; compounds used as polymerization initiators in living cationic polymerization such as t-butanol and 2-phenyl-2-propanol; and the like.

In the present invention, the acidic compound is added in an amount of 0.0 to 100 parts by weight of the ring-opening (co) polymer used in the present invention.
It is modified using 1 to 1000 parts by weight, preferably 0.1 to 100 parts by weight. Generally, the cyclization reaction is performed in a homogeneous system.

When the cyclization is carried out in a homogeneous system, the solvent used is a solvent capable of dissolving the ring-opening (co) polymer, and is not particularly limited as long as it is inert to the cyclization reaction.
Halogen aromatic hydrocarbons such as dichlorobenzene, toluene, nitrobenzene, cyclohexane and the like can be used, and the concentration of the polymer is 0.1 to 30% by weight, preferably 1 to 20% by weight. If the concentration is too high, a reaction between molecules may occur, and if the concentration is too low, efficiency is poor, such as the yield is too small. The reaction temperature is 0 to 200 ° C,
Preferably it is 10-150 degreeC. If the temperature is too low, the reaction will not proceed, and if the temperature is too high, the reaction will be too vigorous and difficult to control. Reaction temperature, reaction time, type of acidic compound,
The conversion amount and conversion rate from the repeating structural unit represented by the general formula 2 to the repeating structural unit represented by the general formula 3 can be controlled by the amount and the like.

The cyclization in the present invention is carried out while consuming double bonds in the main chain structure of the polymer.
~ 90%, preferably 15-85%, more preferably 2
It should be 0-80%. For example, when the repeating structural unit represented by the general formula 2 in the polymer accounts for 50% of all the repeating structural units, all the repeating structural units represented by the general formula 2 are represented by the general formula 3. It may be converted to a unit, but when all the repeating structural units are the repeating structural units represented by the general formula 2, that is, in the case of a homopolymer, all of them are converted to the repeating structural units represented by the general formula 3. Can not. If the residual ratio of double bonds is too high, the heat resistance is insufficient, and if it is too low, the mechanical strength decreases. The residual ratio of double bonds can be controlled by processing conditions such as the concentration of the acidic compound and the processing time. For example, the longer the processing time, the higher the residual ratio of double bonds. Also, the change in the remaining amount of double bonds is
^{In 1} H-NMR, absorption by a proton derived from a phenyl group around 8.0 to 6.6 cm ^−1, absorption by a proton from a carbon-carbon double bond around 6.5 to 4.5 cm ⁻¹ , and 4. It can be measured by a change in absorption due to a proton derived from a saturated bond around ^{1 to} 0.7 cm ^-1 .

The ring-opened (co) polymer cyclized product of the present invention comprises 25
The intrinsic viscosity [η] measured in decalin or toluene at a temperature of 0.05 to 20 dl / g, more preferably 0.1 to 10 dl / g, and 0.2 to 5 dl / g. If the intrinsic viscosity is too small, the mechanical strength will be poor, and if it is too large, the moldability will be poor.

The ring-opened (co) polymer before cyclization used in the present invention is excellent in heat resistance. However, the cyclized thermoplastic ring-opened (co) polymer of the present invention further has a glass transition temperature (hereinafter referred to as "glass transition temperature"). ,
Tg). Although the width of the increase in Tg varies depending on the monomer used, the higher the cyclization ratio, the higher the Tg, and the Tg is preferably 5 ° C or higher, more preferably 10 ° C or higher.

(Hydrogenation reaction) In the present invention, the cyclized product is hydrogenated. The hydrogenation method is not particularly limited, and may be a known method for hydrogenating a general norbornene-based ring-opening polymer. For example, homogeneous catalysts such as Wilkinson complex, cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum,
Presence of heterogeneous catalysts, such as diatomaceous earth, magnesia, alumina, silica, alumina-magnesia, silica-magnesia, silica-alumina, synthetic zeolite, activated alumina, etc., on which a catalytic metal such as nickel, palladium or platinum is supported. The cyclized product may be brought into contact with hydrogen gas below.

In particular, in order to reduce the amount of impurities,
Used as adsorbent for reactive alumina, synthetic zeolite, etc.
0.5cm pore volume^Three/ G or more, preferably 0.7
cm^Three / G or more, and preferably 250 cm in specific surface area^Two/
It is preferable to use a heterogeneous catalyst in which a catalyst metal is
Particularly, the particle diameter is particularly easy to remove by filtration or centrifugation.
2 μm or more, that is, those with a particle size of less than 0.2 μm
Is preferably substantially free from.

In the hydrogenation, the residual ratio of double bonds in the polymer main chain structure before cyclization is 5% or less, preferably 1% or less, more preferably 0% or less, in order to prevent deterioration due to air oxidation. Hydrogen is added so as to be 0.5% or less. The hydrogenation rate can be controlled by the reaction time, reaction temperature, hydrogen pressure and the like. Since it is preferable that the stability to air oxidation and the like is as high as possible, the aromatic ring structure in the cyclized structure is generally hydrogenated. However, the aromatic ring structure is relatively stable, is considerably stable to air oxidation, and a transparent resin having an aromatic ring structure generally has a high refractive index. Hydrogen may be added so as to remain. By selecting a hydrogenation catalyst from a heterogeneous catalyst combining a transition metal compound and an alkyl metal compound, it is possible to saturate only the other unsaturated bonds by hydrogenation while leaving the aromatic ring structure. is there. By analyzing the ₁ H-NMR absorption spectrum, the hydrogenation rate of the main chain structure and the hydrogenation rate of the aromatic ring structure can be determined separately.

(Hydrogenated product) The thermoplastic phenyl-norbornene-based ring-opening (co) polymer cyclized hydrogenated product of the present invention comprises 25
The intrinsic viscosity [η] measured in decalin or toluene at a temperature of 0.05 to 20 dl / g, preferably 0.1 to 20 dl / g.
10 to 10 dl / g, more preferably 0.2 to 5 dl / g. If the intrinsic viscosity is too small, the mechanical strength will be poor, and if it is too large, the moldability will be poor.

The thermoplastic phenyl-norbornene ring-opening (co) polymer cyclized hydrogenated product of the present invention has a higher Tg than the resin before cyclization. Depending on the amount of the cyclized repeating structural unit, the range of increase in Tg varies, but the increase in Tg is 5%.
It is preferably at least 10 ° C, more preferably at least 10 ° C.

(Additives) Various additives may be added to the cyclized hydrogenated phenyl-norbornene-based ring-opening (co) polymer of the present invention, if necessary. Examples of additives used include, for example, antioxidants such as phenol-based and phosphorus-based agents; antistatic agents; ultraviolet absorbers; light stabilizers;
Lubricant; Flame retardant; Pigment; Dye; Antiblocking agent; Polybutadiene, Polyisoprene, Styrene
Rubber-like polymers such as butadiene-styrene block polymers; thermoplastic resins such as petroleum resins, polyethylene, and polypropylene; fibrous fillers such as glass fiber and carbon fiber; particulate fillers such as silica, alumina, and talc; 2- (3,5-di-t-butyl-4-hydroxyphenyl) ethyl propionate] antioxidants such as methane and 2,6-di-t-butyl-4-methylphenol; fluorinated nonionic surfactant Agents, special acrylic resin-based leveling agents, silicone-based leveling agents and the like.

The thermoplastic phenyl-norbornene ring-opening (co) polymer cyclized hydrogenated product of the present invention can be blended with another resin, if necessary. The resin to be blended is not particularly limited, and may be compatible or incompatible with the thermoplastic phenyl-norbornene-based ring-opening (co) polymer cyclized hydrogenated product.

In order to avoid elution from the hydrogenated resin of the present invention, it is preferable that these additives have a large molecular weight and that the additives be small in amount.

(Molding) The thermoplastic phenyl-norbornene ring-opening (co) polymer cyclized hydrogenated product of the present invention can be produced by a known method, for example, injection molding, extrusion molding, cast molding, or the like.
It can be formed by inflation molding, blow molding, vacuum molding, press molding, compression molding, rotational molding, cutting molding, or the like.

The thermoplastic hydrogenated product of the present invention is useful in a wide range of fields as various molded articles including optical materials. For example, optical materials such as an optical lens, a prism, a light diffusion plate, an optical card, an optical fiber, an optical mirror, a liquid crystal display element substrate, a light guide plate, a polarizing film, a retardation film; a liquid medicine container for injection, an ampule, a prefilled syringe, Liquid or powder such as infusion bags, solid medicine containers, eye drop containers, eye drop containers, solid drug containers, food containers, sampling tubes for blood tests, drug container caps, blood collection tubes, sample containers, etc. Experiments on sample containers, medical instruments such as syringes, sterile containers such as medical instruments such as scalpels, forceps, gauze, contact lenses, beakers, petri dishes, flasks, test tubes, centrifuge tubes, etc.
Analytical instruments, medical optical components such as plastic lenses for medical tests, medical infusion tubes, piping materials such as pipes, joints, valves, artificial organs and parts such as denture bases, artificial hearts, artificial roots, etc., chemicals for a long time Medical equipment such as medicine bottles, prefilled syringes, sealed medicine bags, press-through packages, ophthalmic containers, ampules, vials, ophthalmic containers, especially for storing liquid medicines; tanks, trays, carriers, cases, etc. Containers for processing and transport, protective materials such as carrier tapes, separation films, etc., pipes such as pipes, tubes, valves, shippers, flow meters, filters, pumps, and liquids such as sampling containers, bottles, ampules, bags, etc. Equipment for processing electronic components such as containers; coating materials for electric wires and cables; consumer and industrial electronic equipment; copying , Computers, printers, copiers photosensitive drum, OA equipment and the like, instruments,
General insulating materials such as rigid printed circuit boards, flexible printed circuit boards, multilayer printed wiring boards, etc., especially high frequency circuit boards for satellite communication equipment that require high frequency characteristics; liquid crystal substrates, optical memory, automobile and aircraft Equipment for transparent conductive films such as surface heating elements such as defrosters, electric and conductive encapsulants and parts such as transistors, ICs, LSIs, and LEDs, and encapsulants for electric and electronic parts such as motors, capacitors, switches, and sensors Insulation materials such as body materials for TVs and video cameras, structural members for parabolic antennas, flat antennas, and radar domes; automotive parts such as head-up displays, room mirrors, door mirrors, and tail lamp covers; cosmetic containers, food containers, Packaging materials such as microwave oven containers; Etc., and the like.

(Optical Material) The cyclized (hydrogenated) product of the ring-opened (co) polymer of the present invention has a thickness of 400 to 1.2 mm on a plate.
A light transmittance of 830 nm light is 70% or more, preferably 80% or more, more preferably 90% or more, and a retardation value representing birefringence is 10% in a plate having a thickness of 1.2 mm.
0 nm or less, preferably 50 nm or less, more preferably 30 nm or less.
% Or less and 0.05% or less, and has performance suitable as an optical material.

(Medical Equipment) The ring-opened (co) polymer cyclized (hydrogenated) product of the present invention has a thickness of 2 m in addition to the above-mentioned properties.
The light transmittance of the light of 400 to 700 nm on the
0% or more, preferably 50% or more, more preferably 60%
% Or more, has little adsorption of chemicals having polar groups such as alcohols, amines and esters, has a small amount of eluted organic substances, and has properties such as being disposable because it can be easily incinerated. Suitable as medical equipment.

(Electrically Insulating Material) The ring-opened (co) polymer cyclized (hydrogenated) product of the present invention has a volume resistivity of 10 ¹⁶ Ωcm or more, preferably 5 × 10 ¹⁶ , in addition to the aforementioned characteristics. Ω
cm or more and a dielectric constant of 10 ² Hz, 10 ⁶ Hz, 10
^At any frequency of ⁹ Hz, it is 3 or less, preferably 2.5 or less, and the dielectric loss tangent is 10 ² Hz, 10 ⁶
Hz and 10 ⁹ Hz, 10 ^-3
Hereinafter, it has properties such as preferably 7 × 10 ⁻⁴ and is suitable as an electric insulating material.

(Equipment for Processing Electric Parts) The ring-opened (co) polymer cyclized (hydrogenated) product of the present invention has, in addition to the above-mentioned characteristics, a wafer production of an acid other than concentrated sulfuric acid and many organic solvents. It is suitable for electronic parts processing equipment, for example, it has resistance to almost all kinds of chemicals used for.

[0032]

EXAMPLES Reference Examples, Examples and Comparative Examples will be given below.
The present invention will be described more specifically. The amount of conversion from the repeating structural unit represented by the general formula 2 to the repeating structural unit represented by the general formula 3 is determined by ¹ H-NMR using a proton derived from a phenyl group and a proton derived from a carbon-carbon double bond. And the change in the absorption of protons derived from the saturated bonds (in the following examples, the range in which the absorption peak was actually observed was described). The hydrogenation rate is also determined by the change in the absorption of protons derived from unsaturated bonds before and after hydrogenation. The intrinsic viscosity [η] is determined in toluene at 25 ° C (however, when the resin is not dissolved in toluene, ), Tg was measured by a DSC method, the retardation value was measured by a double pass method with a wavelength of 830 nm, and the light transmittance was measured by using an absorptiometer.

Reference Example 1 60 parts by weight of 2-phenyl-5-norbornene was charged into a nitrogen-replaced glass reactor, and used as a molecular weight regulator.
1 part by weight of hexene-1 was added. After the solution was heated to 40 ° C., 10 parts by weight of a 15% by weight solution of triethylaluminum in toluene, 5 parts by weight of triethylamine, and 10 parts by weight of a 20% by weight solution of titanium tetrachloride in toluene were added as a polymerization catalyst to open the ring. The polymerization was started. When the reaction was carried out for 1 hour while maintaining the temperature of the solution at 40 ° C., 5 parts by weight of methanol was added to stop the reaction. 500 parts by weight of strongly stirred acetone and 500 parts of isopropyl alcohol
The polymer was precipitated by pouring the reaction solution into parts by weight of the mixed solution, and collected by filtration. After further washing with 200 parts by weight of acetone, 1
It was dried at 00 ° C. for 24 hours to obtain 50 parts by weight of a polymer.

The intrinsic viscosity of this polymer is 0.42 dl /
g and Tg were 95 ° C. In the ¹ H-NMR (30 ° C. in chloroform-d ₁ ) spectrum, 7.
A proton bonded to a benzene ring at 5-6.3 ppm,
The absorption based on the proton bonded to the unsaturated carbon of the -HC = CH- group at 5.9 to 4.2 ppm, and the absorption based on the proton bonded to the saturated carbon at 4.0 to 0.5 ppm at an intensity ratio of 5: 2: 7. It was observed that the obtained polymer was a ring-opened polymer of 2-phenyl-5-norbornene.

Reference Example 2 Instead of 60 parts by weight of 2-phenyl-5-norbornene, 45 parts by weight of 2-phenyl-5-norbornene and 4,7-
Methano-3a, 4,7,7a-tetrahydroindene 1
Except that 5 parts by weight of the mixture was used, 51 parts by weight of a polymer was obtained in the same manner as in Reference Example 1.

The intrinsic viscosity of this polymer is 0.42 dl /
g and Tg were 108 ° C. In the ¹ H-NMR (30 ° C. in chloroform-d ₁ ) spectrum,
Protons bonded to the benzene ring at 7.5 to 6.3 ppm, protons bonded to the unsaturated carbon of the -HC = CH- group at 5.9 to 4.2 ppm, and bonded to the saturated carbon at 4.0 to 0.5 ppm About 34:26:
73, and the resulting polymer was 2-phenyl-5-norbornene and 4,7-methano-3a, 4,4.
Weight ratio of 7,7a-tetrahydroindene about 44:16
It was confirmed that this was a ring-opened polymer.

Reference Example 3 In place of 2-phenyl-5-norbornene,
Using (3′-bromophenyl) -5-norbornene,
Except that o-dichlorobenzene was used instead of toluene, the procedure of Reference Example 1 was repeated to obtain 50 parts by weight of a polymer.

The intrinsic viscosity of this polymer is 0.40 dl /
g and Tg were 102 ° C. In the ¹ H-NMR (30 ° C. in chloroform-d ₁ ) spectrum,
A proton bonded to a benzene ring at 7.3 to 6.3 ppm, a proton bonded to an unsaturated carbon of -HC = CH- group at 6.2 to 4.4 ppm, and a saturated carbon to 4.1 to 0.6 ppm Absorption based on the resulting protons was observed at an intensity ratio of about 4: 2: 7, and it was confirmed that the obtained polymer was a ring-opened polymer of 2- (3′-bromophenyl) -5-norbornene.

Example 1 100 parts by weight of the polymer obtained in Reference Example 1 and 900 parts by weight of toluene were placed in a nitrogen-substituted glass reactor, and heated to 50 ° C. While stirring, 5 parts by weight of aluminum chloride was added, and the mixture was reacted at a reaction temperature of 50 ° C. for 5 hours.
The reaction solution was put into 2,000 parts by weight of isopropyl alcohol with stirring, and the precipitated polymer was collected.
Drying under reduced pressure of not more than rr for 24 hours gave about 94 parts by weight of a colorless resin.

The limiting viscosity of this resin is 0.41 dl / g,
Tg was 141 ° C. In the ¹ H-NMR (chloroform-d ₁ , 30 ° C.) spectrum, 7.5
-6.3 ppm, 5.9-4.2 ppm, 4.0-0.0 ppm.
An absorption of 5 ppm was observed at an intensity ratio of about 48:16:76, and the obtained resin was cyclized to a residual rate of double bonds in the main chain structure of the resin of Reference Example 1 of about 79%. Was confirmed.

30 parts by weight of this resin was dissolved in 70 parts by weight of toluene, and a nickel catalyst supported on alumina (0.35 parts by weight of nickel, 0.2 parts by weight of nickel oxide, and a pore volume of 0.8 cm ^{3 in} 1 part by weight of the catalyst) / G, specific surface area 300 m ² /
g) 1 part by weight and 2 parts by weight of isopropyl alcohol are added, and the mixture is placed in an autoclave at 230 ° C. and a hydrogen pressure of 50 kg / c.
The reaction was performed at m ² for 5 hours. After completion of the reaction, the catalyst was removed by filtration, the reaction solution was stirred into 500 parts by weight of isopropyl alcohol, and the precipitated polymer was collected and dried at a reduced pressure of 1 torr or less for 24 hours to obtain about 2 parts.
8 parts by weight of a colorless resin were obtained.

The intrinsic viscosity of the resin measured in decalin at 25 ° C. was 0.41 dl / g, and the Tg was 107 ° C.

Further, ¹ H-NMR (chloroform-d
₁ , 30 ° C.) In the spectrum, 7.5-6.3 p
pm to 5.9 to 4.2 ppm, 4.0 to 0.5 ppm were observed at an intensity ratio of 0: 0: 100, and the obtained resin was completely hydrogenated. It was confirmed that the residual ratio of the heavy bond was 0% and the aromatic ring structure was saturated and did not remain.

The hydrogenated product was press-molded at 160 ° C. to produce a disk having a thickness of 1.2 mm and a diameter of 12.5 cm. The light transmittance of this disk is 92 at 400 to 830 nm.
% And the retardation value was 20 nm or less.
The measured using this disc, the volume resistivity of the polymer 5 × 10 ¹⁶ [Omega] cm or more, 10 ²
Hz, 10 ⁶ Hz and 10 ⁹ Hz, the dielectric constant and the dielectric loss tangent were 2.43 and 5 × 10 ⁻⁴ , respectively. From these, it was found that this resin had characteristics suitable as an optical material and an electrical insulating material.

Further, as a result of atomic absorption analysis of a 10% by weight cyclohexane solution of the hydrogenated product, the atomic weight of titanium in the hydrogenated product was 0.01 ppm or less (detection limit), and the atomic weight of nickel was 0.01 ppm (detection limit). ) Further, 100 mg of this hydrogenated product was burned by a Doman burning apparatus, absorbed in 5 ml of pure water, and analyzed by ion chromatography. As a result, the chlorine atom content was 0.02 ppm or less (detection limit).

To 17 parts by weight of the hydrogenated product, 0.008 parts by weight of an antioxidant (Irganox 1010, manufactured by Ciba Geigy) was added, and a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.)
TEM-35B, screw diameter 37 mm, L / D = 3
2. Screw rotation speed 250 rpm, resin temperature 190
At a feed rate of 10 kg / hour).

Using the pellets, injection molding (mold clamping pressure: 350 t, resin temperature: 200 ° C., mold temperature: 70 ° C.)
A transparent container having a diameter of 200 mm, a height of 130 mm, an average thickness of 3 mm and a cylindrical bottom surface, and a size of 100 mm x 50 m
A test piece of mx 2.0 mm was prepared.

When the total light transmittance of the test piece was measured,
The transparency was good at 90.0% or more. The turbidity was measured and found to be 0.1%.

2% by weight of agar was added to an LB medium (an aqueous solution of 1% by weight of bactotryptone, 0.5% by weight of yeast extract, 1% by weight of NaCl, and 0.1% by weight of glucose adjusted to pH 7.5). Gelation by steam sterilization at 121 ° C. for 30 minutes,
ml in a molded container and left at room temperature for 6 hours.
It was capped with an aluminum foil and sterilized by irradiating γ-rays at 25 kGy. Thereafter, the mixture was kept at 37 ° C. for 3 days, but no fungal growth was observed. The appearance of the transparent container after the treatment was good, and no cloudiness, cracks, or deformation was visually observed.

The test piece was immersed in a pH 9 aqueous sodium carbonate solution, pH 4 hydrochloric acid, and ethanol for 48 hours, and the appearance was observed. However, there was no change, and there was no change in turbidity or total light transmittance.

Further, after the test piece was immersed in a pH 9 aqueous sodium carbonate solution, pH 4 hydrochloric acid, and ethanol for 48 hours, the appearance was observed, but there was no change, and turbidity and total light transmittance did not change. Further, test specimens were concentrated sulfuric acid, 30
% Dilute sulfuric acid, 70% nitric acid, phosphoric acid, hydrofluoric acid (hydrofluoric acid 7% by weight, nitric acid 42% by weight, water 51% by weight), 37% hydrochloric acid,
30% aqueous hydrogen peroxide, saturated aqueous potassium hydroxide solution, 29
% Ammonia water, acetone, isopropyl alcohol,
It was immersed in trichloroethylene, a 2.38 wt% TMAHO aqueous solution, and an etching solution for auminium (concentrated phosphoric acid 80 wt%, nitric acid 5 wt%, glacial acetic acid 5 wt%, water 10 wt%) for 5 minutes. Although dissolved in trichlorethylene and carbonized with concentrated sulfuric acid, the surface was not affected by other chemicals, indicating good chemical resistance.

[0052] The test piece having no effect was recognized by 10
After cutting into 20 mm width, 20 g was ultrasonically washed in distilled water for 20 minutes, and then dried at 40 ° C. for 10 hours. The test piece of 20 g was put in a hard glass flask, and 200 g of distilled water was added. The bottle was covered with a hard glass lid and allowed to stand at 50 ° C. for 24 hours to recover distilled water.

As a control, 200 g of distilled water was placed in a hard glass flask, covered with hard glass,
It was left at 24 ° C. for 24 hours.

The amount of elution from the test piece was determined from the difference between the results of analysis of the two types of distilled water by the atomic absorption method, ion chromatography, combustion-non-dispersive infrared gas analysis, and the like. The amount is 0.01 ppm (detection limit) or less, the nickel atom elution amount is 0.01 ppm (detection limit) or less, the chlorine atom elution amount is 0.02 ppm (detection limit) or less, and the total organic carbon amount is 2 ppm (detection limit) or less. Met.

The test piece was subjected to a dissolution test in accordance with the Japanese Pharmacopoeia, 12th Edition, “Plastic Test Method for Infusion Solution”. The bubbling disappeared within 3 minutes, the pH difference was -0.03, the ultraviolet absorption was 0.005, and the potassium permanganate reducing substance was 0.10 ml, and had characteristics suitable for medical equipment.

Example 2 The same treatment as in Example 1 was carried out except that the reaction temperature was 55 ° C. and the reaction time by aluminum chloride treatment was 12 hours.

The resin obtained by treating with aluminum chloride and having 96 parts by weight has an intrinsic viscosity of 0.41 dl / g and a Tg of 16%.
6 ° C. In addition, ¹ H-NMR (chloroform-d ₁
Medium, 30 ° C.) In the spectrum, 7.5 to 6.3 pp
m, an absorption of 5.9 to 4.2 ppm and an absorption of 4.0 to 0.5 ppm were observed at an intensity ratio of about 43: 6: 90. It was confirmed that the residual ratio of heavy bonds was cyclized to about 32%.

Further, 25 of the resin obtained by hydrogenation
C., intrinsic viscosity measured in decalin is 0.41 dl /
g and Tg were 156 ° C. In the ¹ H-NMR (30 ° C. in chloroform-d ₁ ) spectrum,
7.5-6.3 ppm, 5.9-4.2 ppm, 4.0
Absorption of 0.5 to 0.5 ppm was observed at an intensity ratio of 0: 0: 100, the obtained resin was completely hydrogenated, the residual ratio of double bonds in the main chain structure was 0%, and the aromatic ring It was found that the structure was saturated and did not remain.

The hydrogenated product was press-formed at 200 ° C. to produce a disk having a thickness of 1.2 mm and a diameter of 12.5 cm. The light transmittance of this disk is 92 at 400 to 830 nm.
% And the retardation value was 20 nm or less.
The measured using this disc, the volume resistivity of the polymer 5 × 10 ¹⁶ [Omega] cm or more, 10 ²
Hz, 10 ⁶ Hz and 10 ⁹ Hz, the dielectric constant and the dielectric loss tangent were 2.42 and 5 × 10 ⁻⁴ , respectively.

Example 3 An aluminum chloride treatment was carried out in the same manner as in Example 1 except that the reaction temperature was 55 ° C. and the reaction time was 6 hours, to obtain 95 parts by weight of a resin.

The intrinsic viscosity of this resin is 0.41 dl / g,
Tg was 145 ° C. In the ¹ H-NMR (chloroform-d ₁ , 30 ° C.) spectrum, 7.5
-6.3 ppm, 5.9-4.2 ppm, 4.0-0.0 ppm.
Absorption of 5 ppm was observed at an intensity ratio of about 47:14:79, and the obtained resin was cyclized so that the residual ratio of double bonds in the main chain structure of the resin of Reference Example 1 was about 70%. Was confirmed.

A solution prepared by dissolving 20 parts by weight of this resin in 80 parts by weight of toluene and 0.2 part by weight of cobalt (III) acetylacetonate were charged in an autoclave equipped with a stirrer. After replacing the gas part in the autoclave with hydrogen,
An autoclave was charged with 3 parts by weight of a 15% by weight solution of triisobutylaluminum in toluene, and hydrogen pressure was 10 kg.
The reaction was carried out at 80 ° C./cm ² for 1 hour. Acetone 2
The reaction solution was poured while stirring a mixed solution of 50 parts by weight and 250 parts by weight of isopropyl alcohol to precipitate a resin, and the resin was collected by filtration. After further washing with 200 parts by weight of acetone, it was dried at 100 ° C. for 24 hours in a vacuum drier at a reduced pressure of 1 mmHg or less to obtain 19 parts by weight of a resin.

This resin had an intrinsic viscosity of 0.40 dl / g and a Tg of 119 ° C. In addition, ¹ H-NMR
(In chloroform -d _1, 30 ℃) in the spectrum, 7.5~6.3ppm, 5.9~4.2ppm,
An absorption of 4.0 to 0.5 ppm was observed at an intensity ratio of about 47: 0: 93, and the resulting resin had no benzene ring hydrogenated at all, but the residual ratio of double bonds in the main chain structure Is 0
%.

The hydrogenated product was press-formed at 200 ° C. to produce a disk having a thickness of 1.2 mm and a diameter of 12.5 cm. The light transmittance of this disc is 91 at 400 to 830 nm.
% And the retardation value was 20 nm or less.
The measured using this disc, the volume resistivity of the polymer 5 × 10 ¹⁶ [Omega] cm or more, 10 ²
Hz, 10 ⁶ Hz and 10 ⁹ Hz, the dielectric constant and the dielectric loss tangent were 2.43 and 5 × 10 ⁻⁴ , respectively.

Example 4 The ring-opening polymer obtained in Reference Example 2 was used in place of the ring-opening polymer obtained in Reference Example 1, and the reaction time of the aluminum chloride treatment was 1
Except for 0 hour, the same treatment as in Example 1 was performed.

The intrinsic viscosity of the resin obtained by treating with aluminum chloride at 95 parts by weight was 0.41 dl / g and the Tg was 15
7 ° C. In addition, ¹ H-NMR (chloroform-d ₁
Medium, 30 ° C.) In the spectrum, 7.5 to 6.3 pp
m, 5.9 to 4.2 ppm, absorption at 4.0 to 0.5 ppm was observed at an intensity ratio of about 31:18:85, and the obtained resin was found to have two absorptions in the main chain structure of the resin of Reference Example 2. It was confirmed that the residual ratio of heavy bonds was cyclized to about 58.2%.

Further, 25 of the resin obtained by hydrogenation
C., intrinsic viscosity measured in decalin is 0.40 dl /
g and Tg were 156 ° C. In the ¹ H-NMR (30 ° C. in chloroform-d ₁ ) spectrum,
7.5-6.3 ppm, 5.9-4.2 ppm, 4.0
Absorption of 0.5 to 0.5 ppm was observed at an intensity ratio of 0: 0: 100, the obtained resin was completely hydrogenated, the residual ratio of double bonds in the main chain structure was 0%, and the aromatic ring It was found that the structure was saturated and did not remain.

The hydrogenated product was press-formed at 200 ° C. to produce a disk having a thickness of 1.2 mm and a diameter of 12.5 cm. The light transmittance of this disk is 92 at 400 to 830 nm.
% And the retardation value was 20 nm or less.
The volume resistivity of the hydrogenated product was measured to be 5 × 10 ¹⁶ Ωcm or more.
^{0 2 Hz, 10 6 Hz,} 10 9 Hz dielectric constant and dielectric loss tangent respectively 2.42 at any frequency between 5 × 10
^-4 .

Further, as a result of atomic absorption analysis of a 10% by weight solution of the hydrogenated product in cyclohexane, the atomic weight of titanium in the resin was 0.01 ppm or less (detection limit) and the atomic weight of nickel was 0.01 ppm or less (detection limit). Met. Further, 100 mg of this hydrogenated product was burned by a Doman combustion apparatus, absorbed in 5 ml of pure water, and analyzed by ion chromatography.
It was below 02 ppm (detection limit).

To 17 parts by weight of this hydrogenated product, 0.008 parts by weight of an antioxidant (Irganox 1010) was added, and a twin screw extruder (TEM-35B, screw diameter 3) was used.
7mm, L / D = 32, screw rotation speed 250rpm
m, resin temperature 215 ° C., feed rate 10 kg / hour) to obtain pellets.

Using the pellets, injection molding (mold clamping pressure: 350 t, resin temperature: 225 ° C., mold temperature: 70 ° C.)
A transparent container having a diameter of 200 mm, a height of 130 mm, an average thickness of 3 mm and a cylindrical bottom surface, and a size of 100 mm x 50 m
A test piece of mx 2.0 mm was prepared.

When the total light transmittance of the test piece was measured,
The transparency was good at 90.1% or more. The turbidity was measured and found to be 0.1%.

To the molded transparent container, add 300 ml of LB medium and 6 g of agar, cap with aluminum foil,
The mixture was subjected to steam sterilization at 1 ° C. for 30 minutes to be gelled and solidified. After incubation at 37 ° C. for 3 days, no fungal growth was observed. The appearance of the transparent container after the treatment was good, and no cloudiness, cracks, or deformation was visually observed.

The test piece was immersed in a pH 9 sodium carbonate aqueous solution, pH 4 hydrochloric acid, and ethanol for 48 hours, and the appearance was observed, but no change was observed, and turbidity and total light transmittance did not change.

The test piece was cut into a 10 mm width, 20 g of the test piece was ultrasonically washed in distilled water for 20 minutes, and then dried at 40 ° C. for 10 hours. The test piece of 20 g was put in a hard glass flask, and 200 g of distilled water was added. The bottle was covered with a hard glass lid and allowed to stand at 50 ° C. for 24 hours to recover distilled water.

As a control, 200 g of distilled water was placed in a hard glass flask, covered with hard glass,
It was left at 24 ° C. for 24 hours.

The amount of elution from the test piece was determined from the difference between the results of analysis of the two types of distilled water by atomic absorption spectrometry, ion chromatography, combustion-non-dispersive infrared gas analysis, and the like. The amount is 0.01 ppm (detection limit) or less, the nickel atom elution amount is 0.01 ppm (detection limit) or less, the chlorine atom elution amount is 0.02 ppm (detection limit) or less, and the total organic carbon amount is 2 ppm (detection limit) or less. Met.

The test piece was subjected to a dissolution test in accordance with the Japanese Pharmacopoeia, 12th Edition, "Plastic Test Method for Infusion". Foaming disappeared within 3 minutes, pH difference was -0.03, ultraviolet absorption was 0.005, and potassium permanganate reducing substance was 0.11 ml.

Example 5 Instead of the ring-opening polymer obtained in Reference Example 1, the ring-opening polymer obtained in Reference Example 3 was used, the solvent was changed to o-dichlorobenzene, and aluminum chloride was treated with 8 parts by weight of aluminum chloride. The reaction was performed in the same manner as in Example 1 except that the reaction temperature was 60 ° C. and the reaction time was 4 hours.

The intrinsic viscosity of the resin obtained by treating with aluminum chloride in 96 parts by weight was 0.40 dl / g and the Tg was 15
1 ° C. In addition, ¹ H-NMR (chloroform-d ₁
Medium, 30 ° C.) In the spectrum, 7.3-6.3 pp
m is a proton bonded to a benzene ring, 6.2 to 4.4p
The absorption based on the proton bonded to the unsaturated carbon of the -HC = CH- group at pm and the proton bonded to the saturated carbon at 4.1 to 0.6 ppm was observed at an intensity ratio of about 37:15:78 and was obtained. It was confirmed that the obtained resin was cyclized to a residual ratio of double bonds in the main chain structure of the resin of Reference Example 3 of about 73%.

Further, 25 of the resin obtained by hydrogenation
C., intrinsic viscosity measured in decalin is 0.40 dl /
g and Tg were 121 ° C. In the ¹ H-NMR (30 ° C. in chloroform-d ₁ ) spectrum,
7.3 to 6.3 ppm, 6.2 to 4.4 ppm, 4.1
~ 0.6 ppm absorption was observed at an intensity ratio of 0: 0: 100, the resulting resin was completely hydrogenated, the residual ratio of double bonds in the main chain structure was 0%, and the aromatic ring It was found that the structure was saturated and did not remain.

The hydrogenated product was press-formed at 200 ° C. to produce a disk having a thickness of 1.2 mm and a diameter of 12.5 cm. The light transmittance of this disc is 90 at 400 to 830 nm.
% And the retardation value was 20 nm or less.

[0083]

The resin of the present invention has transparency, low birefringence,
It is excellent in heat resistance, low content of transition metal atoms derived from catalysts, electric properties, and the like, and can be used for optical materials, electric insulating materials, medical equipment, electronic parts processing equipment, and the like.

Continuation of the front page (56) References JP-A-50-154399 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 61/06-61/08

Claims (6)

(57) [Claims] 1. Ring opening (co) of phenyl-norbornenes
A hydrogenated cyclized product formed by forming a six-membered ring with the double bond of the main chain of the polymer and the benzene ring of the side chain, and the proportion of the double bond of the main chain consumed by the cyclization is 10-90%
And the ratio of double bonds remaining without hydrogenation is 5
% Or less of a phenyl-norbornene ring-opening (co) polymer, a hydrogenated cyclized product formed by forming a six-membered ring with a double bond in the main chain and a benzene ring in the side chain. 2. Ring opening (co) of phenyl-norbornenes
After the polymer is cyclized to the extent that 10 to 90% of the main chain double bonds remain, the residual ratio of the main chain double bonds of the polymer is 5%.
The method for producing a ring-opened (co) polymer cyclized hydrogenated product according to claim 1, wherein the hydrogenation is carried out as follows. 3. An optical material comprising the thermoplastic phenyl-norbornene-based ring-opening (co) polymer according to claim 1. 4. A medical device comprising the thermoplastic phenyl-norbornene-based ring-opening (co) polymer according to claim 1. 5. An electric insulating material comprising the thermoplastic phenyl-norbornene-based ring-opening (co) polymer according to claim 1. 6. An electronic component processing equipment comprising the thermoplastic phenyl-norbornene-based ring-opening (co) polymer according to claim 1.